WO2017160047A1 - Ｍｎ 또는 Ｃｏ이 도핑된 ＭｇＯ 부분 안정화 지르코니아 고체 전해질 - Google Patents

Ｍｎ 또는 Ｃｏ이 도핑된 ＭｇＯ 부분 안정화 지르코니아 고체 전해질 Download PDF

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WO2017160047A1
WO2017160047A1 PCT/KR2017/002719 KR2017002719W WO2017160047A1 WO 2017160047 A1 WO2017160047 A1 WO 2017160047A1 KR 2017002719 W KR2017002719 W KR 2017002719W WO 2017160047 A1 WO2017160047 A1 WO 2017160047A1
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stabilized zirconia
partially stabilized
solid electrolyte
doped
mgo partially
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French (fr)
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이희수
전설
류지승
김부영
조승현
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University Industry Cooperation Foundation of Pusan National University
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University Industry Cooperation Foundation of Pusan National University
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Priority to JP2018548738A priority Critical patent/JP6724157B2/ja
Priority to US16/084,733 priority patent/US20190084886A1/en
Publication of WO2017160047A1 publication Critical patent/WO2017160047A1/ko
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Definitions

  • the present invention relates to a solid electrolyte comprising MgO partially stabilized zirconia doped with at least one of Mn and Co.
  • deoxidation should be able to quickly and directly measure the oxygen concentration in molten steel in converters, ladles or tundish whenever desired.
  • the measurement method using a metallurgical oxygen sensor in molten steel is widely used for measuring dissolved oxygen in molten steel because it can quickly and accurately measure and analyze oxygen activity in an in-suit.
  • MgO partially stabilized zirconia solid electrolyte which exhibits excellent thermal shock resistance that can be used in molten steel of 1600 ° C. or higher, has been widely used as a solid electrolyte material for measuring dissolved oxygen in molten steel.
  • the ZrO 2 -based solid electrolyte has a cubic phase at a temperature of 2370 ° C. or higher, a tetragonal phase in the range of 2370-1170 ° C., and a monoclinic phase at 1170 ° C. or lower.
  • Zr + 4 in position to be applied to the solid electrolyte material Y 3+, Ca 2 +, Mg 2 + e is the low to ions are substituted, such as, but to try to form the oxygen vacancies, in consideration of more than 1500 °C operation process
  • lattice deformation caused by thermal shock deteriorates ion conductivity and phase stability.
  • the invention relates to a solid electrolyte comprising MgO partially stabilized zirconia doped with at least one of Mn and Co.
  • the doping of any one of Mn and Co includes the formation of oxygen vacancies by one or more of Mn and Co being substituted at the zirconium position.
  • the formation of oxygen vacancy shows superior ionic conductivity compared to undoped MgO partially stabilized zirconia.
  • the MgO partially stabilized zirconia doped with Mn or Co is present only in the cubic phase at room temperature, and thus exhibits excellent stability of maintaining the cubic phase at room temperature and at a temperature of 1500 ° C. or higher.
  • the present invention provides a dissolved oxygen amount sensor in molten steel of 1500 °C or more comprising the solid electrolyte.
  • the solid electrolyte of the present invention can be used as a solid electrolyte in a high temperature environment by providing cubic phase stability and high ion conductivity even at high temperatures.
  • the present invention provides a method of making Mn and Co doped MgO partially stabilized zirconia comprising mixing MgO partially stabilized zirconia powder and manganese oxide or cobalt oxide powder and sintering the mixture.
  • the ratio of the MgO partially stabilized zirconia powder and manganese oxide or cobalt oxide powder is characterized in that 1: 5 to 1:10.
  • Mixing the powder includes ball milling the MgO partially stabilized zirconia powder and manganese oxide or cobalt oxide powder in a solvent.
  • the solvent may preferably be an alcohol solvent.
  • the binder may preferably be polyvinyl alcohol.
  • Example One MgO Partial stabilization Zirconia Powder manufacturing
  • a mixed solution was prepared with ZrCl 2 and MgCl 2 ⁇ 2H 2 O.
  • the mixed solution was added to an ultrasonic stirrer and stirred at 250 rpm to add ammonia solution until the pH was 10. The precipitate precipitated out. Then, the mixture was stirred for 2 to 3 hours at a speed of 300 rpm.
  • the coprecipitate was then filtered while the stirred mixed solution was washed with ethanol and distilled water. The filtered precipitate was dried at 100 ° C. for 12 hours and subsequently calcined at 600 ° C. for 2 hours.
  • the MgO partially stabilized zirconia powder prepared in Example 1 was prepared.
  • Mn 2 O 3 powder was mixed with the MgO partially stabilized zirconia powder in a 1: 1 molar ratio, and zirconia ball ball milling was performed at 300 rpm for 24 hours using ethanol as a solvent.
  • the polyvinyl alcohol (PVA) binder was mixed with the ball milled powder in a ratio of 10: 1 wt%.
  • the mold (disc type: 20 ⁇ , 2g ⁇ bar type: 60mm x 70 mm, 3g) was put into uniaxial pressure molding (20 Mpa, 1 m 30 s). Subsequently, the obtained molded product was raised at a temperature increase rate of 5 ° C./min and held at 500 ° C. for 1 hour to remove the binder, and sintered at 1600 ° C. for 6 hours.
  • Example 2 The same procedure was followed in Example 2 except that the molar ratio of MgO partially stabilized zirconia powder and Mn 2 O 3 powder was 1: 5.
  • Example 2 The same procedure was followed in Example 2 except that the molar ratio of MgO partially stabilized zirconia powder and Mn 2 O 3 powder was set to 1:10.
  • Example 2 The same procedure was followed in Example 2 except that the molar ratio of MgO partially stabilized zirconia powder and Mn 2 O 3 powder was 1:15.
  • the Pt wire electrode was wound at 1 cm intervals on the solid electrolyte for measuring ion conductivity prepared in Examples 1 to 5, Pt paste was applied to the place where the electrode was wound, and then fired at 900 ° C. for 1 hour, and the ion conductivity was obtained by direct current 4-terminal method. It was measured and the phase stability was evaluated as follows.
  • phase transition occurs from 1200 ° C. to tetragonal and 2370 ° C. to the cubic phase, which causes a phase shift when used in an oxygen measuring sensor in a molten steel of 1500 ° C. or higher.
  • FIG. 1 in the case of Example 1, in which Mn is not doped, the peak of the monoclinic phase in addition to the cubic phase is observed at room temperature as in the conventional problem, and thus phase transition to the monoclinic can be observed. .
  • Examples 2 to 5 corresponding to the present invention doped with Mn, it was confirmed that only the peak of the cubic phase, which is hardly observed in the monoclinic phase, was observed, which showed phase stability according to the temperature between the high temperature and the low temperature. The case of the invention has been proven.

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  • Compositions Of Oxide Ceramics (AREA)

Abstract

본 발명은 Mn 및 Co 중 어느 하나 이상이 도핑된 MgO 부분 안정화 지르코니아를 포함하는, 고체 전해질에 관한 것이다.

Description

Ｍｎ 또는 Ｃｏ이 도핑된 ＭｇＯ 부분 안정화 지르코니아 고체 전해질
본 발명은 Mn 및 Co 중 어느 하나 이상이 도핑된 MgO 부분 안정화 지르코니아를 포함하는, 고체 전해질에 관한 것이다.
제강공정에서 C, Si, P 등의 불순물을 산화 정련하기 위해 용철에 흡입 되어지는 산소는 정련이 진행됨에 따라 용존량이 점차 증가하게 된다. 용존하는 산소는 기포 및 산화물 등의 개재물을 형성시켜 철강(또는 구리 금속)의 품질을 크게 저하시킨다. 이러한 용존 산소를 제거하기 위하여 탈산제나 합금 원소를 첨가시켜 탈산을 행하게 되는데 용융 금속의 산소농도 제어는 철강제품의 중요한 품질관리 항목이다.
제강공정에서 탈산은 전로, 래들(ladle) 또는 턴디쉬(tundish) 내 용강 중의 산소농도를 원하는 때마다 신속하게 직접 측정할 수 있도록 해야 한다. 용강 내 용존산소량 측정 센서(Metallurgical Oxygen sensor)를 이용한 측정법은 산소활량을 in-suit로 신속정확하게 측정 분석할 수 있기 때문에 용강내 용존 산소량 측정에 많이 사용되고 있다.
용강 내 용존산소량 측정 센서용 고체 전해질 재료로써 1600℃ 이상의 용강에서 사용될 수 있는 우수한 내열 충격성을 나타내는 MgO 부분 안정화 지르코니아 고체 전해질이 널리 사용되고 있다.
그런데, 이 안정화 지르코니아계 고체 전해질은 아래와 같은 문제점이 있다. ZrO2계 고체 전해질은 2370℃ 이상의 온도에서는 큐빅(cubic) 상이고, 2370 ~ 1170℃ 영역에서는 테트라고날(tetragonal) 상이며, 1170℃ 이하에서는 모노클리닉(monoclinic) 상으로 존재하는 특징을 지닌다.
고체 전해질 재료로 적용되기 위해 Zr4 + 위치에 Y3+, Ca2 +, Mg2 + 등과 같은 전자가가 낮은 이온들이 치환하여 산소 공공을 형성함을 시도하고 있지만, 1500℃ 이상의 조업 공정을 고려한 Metallurgical oxygen sensor용 고체 전해질 재료로 사용할 경우 열 충격에 의한 격자 변형으로 이온전도성 및 상 안정성이 저하된다.
일 측면으로서, 본 발명은 Mn 및 Co 중 어느 하나 이상이 도핑된 MgO 부분 안정화 지르코니아를 포함하는, 고체 전해질에 관한 것이다.
여기서, Mn 및 Co 중 어느 하나의 도핑은 Mn 및 Co 중 어느 하나 이상이 지르코늄 위치에 치환되어 산소 공공이 형성을 포함한다. 이러한 산소 공공 형성에 의해 도핑되지 않은 MgO 부분 안정화 지르코니아에 비해 우수한 이온전도성을 보인다.
상기 Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아는 실온에서 큐빅상(cubic)으로만 존재함을 특징으로 하여, 실온 및 1500℃ 이상의 온도에서 큐빅상(cubic)을 유지하는 우수한 안정성을 보인다.
다른 측면으로서, 본 발명은 상기 고체 전해질을 포함하는 1500℃ 이상의 용강 내 용존 산소량 측정 센서를 제공한다.
본 발명의 고체전해질은 고온에서도 큐빅상 안정성 및 높은 이온전도특성을 제공하여 고온 환경에서의 고체전해질로 사용가능하다.
다른 측면으로서, 본 발명은 MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말을 혼합하고, 상기 혼합물을 소결함을 포함하는, Mn 및 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법을 제공한다.
상기 MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말의 비는 1:5 내지 1:10임을 특징으로 한다.
Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
분말의 혼합은, MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말을 용매 내에서 볼밀링을 함을 포함한다. 상기 용매는 바람직하게는 알코올 용매일 수 있다.
상기 소결 단계 전에 상기 분말을 바인더와 함께 혼합하고 상기 가압 성형 후 상기 바인더를 고온에서 제거함을 포함한다. 상기 바인더는 바람직하게는 폴리비닐알코올일 수 있다.
도 1은, 본 발명의 실시예들의 결정구조 변화를 보여준다.
도 2는, 본 발명의 실시예들의 이온전도도를 보여준다.
이하, 첨부한 도면을 참조하여 본 발명의 실시예에 대해 상세히 설명한다. 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는바, 특정 실시예들을 도면에 예시하고 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 각 도면을 설명하면서 유사한 참조부호를 유사한 구성요소에 대해 사용하였다.
본 출원에서 사용한 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
실시예 1: MgO 부분 안정화 지르코니아 분말 제조
8 mol%의 MgPSZ 분말을 합성하기 위해서 ZrCl2와 MgCl2·2H2O로 혼합 용액을 제조하였고, 이 혼합 용액을 초음파 교반기 넣고 250 rpm 으로 교반하면서 암모니아 용액을 pH 10이 될 때까지 첨가하여 공침물을 침전시켰다. 그 후 300 rpm의 속도로 2~3시간 동안 교반하였다. 이후 교반한 혼합 용액을 에탄올 및 증류수로 세척하면서 공침물을 여과시켰다. 여과된 침전물을 100℃에서 12 시간 동안 건조시키고, 후속하여 2 시간 동안 600℃에서 하소시켰다.
실시예 2
실시예 1에서 제조된 MgO 부분 안정화 지르코니아 분말을 준비하였다. 이 MgO 부분 안정화 지르코니아 분말에 Mn2O3 분말을 1:1 몰비율로 혼합하고, 에탄올을 용매로 하여 지르고니아 볼로 볼밀링을 300 rpm으로 24시간 동안 하였다. 볼밀링된 혼합 분말에 폴리비닐알코올(PVA: Poly Vinyl Alcohol) 바인더를 10:1 중량%의 비율로 혼합하였다. 이후 몰드(disc type: 20 Ø, 2g · bar type: 60mm x 70 mm, 3g)에 넣고 일축가압성형(20 Mpa, 1 m 30 s)하였다. 후속하여 얻어진 성형체를 5℃/분의 승온 속도로 온도를 상승시키고 500℃에서 1시간 동안 유지하여 바인더를 제거하고, 1600℃에서 6시간 동안 소결하였다.
실시예 3
실시예 2에서 MgO 부분 안정화 지르코니아 분말과 Mn2O3 분말의 몰비율을 1:5로 한 것을 제외하고는 동일하게 하였다.
실시예 4
실시예 2에서 MgO 부분 안정화 지르코니아 분말과 Mn2O3 분말의 몰비율을 1:10으로 한 것을 제외하고는 동일하게 하였다.
실시예 5
실시예 2에서 MgO 부분 안정화 지르코니아 분말과 Mn2O3 분말의 몰비율을 1:15으로 한 것을 제외하고는 동일하게 하였다.
특성평가
실시예 1 내지 5에서 제조된 이온 전도성 측정용 고체 전해질에 1cm 간격으로 Pt 와이어 전극을 감고 전극을 감은 자리에 Pt 페이스트를 도포한 후 900℃에서 1시간 소성하여 이를 직류 4단자 법으로 이온 전도성을 측정하였고, 상안정성을 아래와 같이 평가하였다.
이온 전도성 및 Cubic 상 안정성 평가
지르코니아계 고체 전해질은 상온에서 모노클리닉 상으로 존재할 경우, 1200℃부터 테트라고날, 2370℃부터 큐빅상으로 상전이가 일어나기 때문에 1500℃ 이상의 용강내 산소 측정 센서에 사용될 때 상변이가 이뤄지는 문제가 있다. 도 1에서 확인되는 바와 같이, Mn이 도핑되지 않은 실시예 1의 경우는 종래의 문제점과 같이 상온에서 큐빅상 이외에 모노클리닉(monoclinic) 상의 피크가 관찰되어 모노클리닉으로의 상변이를 관찰할 수 있다. 그러나, Mn이 도핑된 본 발명에 해당하는 실시예 2 내지 5의 경우는 모노클리닉 상은 거의 관찰할 수 없는 큐빅상의 피크만 관찰됨을 확인할 수 있었고, 이는 고온과 저온 사이의 온도에 따른 상안정성이 본 발명의 경우는 입증되었다.
또한, 도 2에서 확인되는 바와 같이, Mn이 도핑된 Mg-PSZ 고체 전해질(0.732 S·cm-1)은 그렇지 않은 고체 전해질(0.392 S·cm-1)에 비해 약 1.5 배 향상된 이온 전도도를 보여주었다. 이는 망간 및 코발트 첨가에 의한 산소공공 형성에 따라 전하 운반체(charge carrier) 농도가 증가하기 때문으로 판단한다.

Claims (12)

  1. Mn 및 Co 중 어느 하나 이상이 도핑된 MgO 부분 안정화 지르코니아를 포함하는, 고체 전해질.
  2. 제1항에 있어서,
    상기 Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아는 Mn 및 Co 중 어느 하나 이상이 지르코늄 위치에 치환되어 산소 공공이 형성됨을 특징으로 하는,
    고체 전해질.
  3. 제1항에 있어서,
    상기 Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아는 실온에서 큐빅상(cubic)으로만 존재함을 특징으로 하는,
    고체 전해질.
  4. 제1항에 있어서,
    상기 Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아는 Mn 또는 Co가 도핑되지 않은 MgO 부분 안정화 지르코니아에 비해 이온전도가 향상됨을 특징으로 하는,
    고체 전해질.
  5. 제1항 내지 제4항 중 어느 하나의 고체 전해질을 포함하는 용강 내 용존 산소량 측정 센서.
  6. 제1항 내지 제4항 중 어느 하나의 고체 전해질을 포함하는 1500℃ 이상의 온도에서 이온전도도를 측정하는 이온전도측정 센서.
  7. MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말을 혼합하고,
    상기 혼합물을 소결함을 포함하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
  8. 제7항에 있어서,
    상기 MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말의 비는 1:5 내지 1:10임을 특징으로 하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
  9. 제7항에 있어서,
    분말의 혼합은, MgO 부분 안정화 지르코니아 분말 및 망간산화물 또는 코발트산화물 분말을 용매 내에서 볼밀링을 함을 포함하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
  10. 제9항에 있어서,
    상기 용매는 알코올 용매임을 특징으로 하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
  11. 제9항에 있어서,
    상기 소결 단계 전에 상기 분말을 바인더와 함께 혼합하고 상기 가압 성형 후 상기 바인더를 고온에서 제거함을 포함하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
  12. 제11항에 있어서,
    상기 바인더는 폴리비닐알코올임을 특징으로 하는,
    Mn 또는 Co가 도핑된 MgO 부분 안정화 지르코니아를 제조하는 방법.
PCT/KR2017/002719 2016-03-14 2017-03-14 Ｍｎ 또는 Ｃｏ이 도핑된 ＭｇＯ 부분 안정화 지르코니아 고체 전해질 Ceased WO2017160047A1 (ko)

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